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In the binuclear copper(II) title complex, [Cu2(C9H7O4)4(C2H3N)2], an inversion centre is situtated at the mid-point of the Cu—Cu bond. The CuII atom together with its four coordinated O atoms are in a distorted planar square arrangement while the nitro­gen and the other CuII atom are located in apical positions. The whole mol­ecule looks like a paddle-wheel. In the crystal, chains are assembled along the b axis through C—H...O hydrogen bonds and slipped π–π inter­actions between the benzene rings of neighbouring mol­ecules [centroid–centroid distance = 3.6929 (3) Å and slippage = 0.641 (1) Å].

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In the title compound, [Ag6(C12H10N3OS)6]·4C3H7NO, the hexa­nuclear complex mol­ecule lies about an inversion center. The six Ag atoms form a distorted octa­hedron, with Ag...Ag distances in the range 2.933 (1)–3.401 (1) Å. Each Ag atom is surrounded by one N atom and two thiol­ate S atoms from two deprotonated 2-hy­droxy-1-naphthaldehyde thio­semi­carb­a­zone ligands. Each ligand coordinates three Ag atoms via a bridging thiol­ate S atom and a monodentate N atom, thus two Ag3S3 hexa­gonal rings are linked together. Two dimethyl­formamide solvent mol­ecules are located in four sets of sites with half-occupancy and form O...H—N hydrogen bonds to the complex mol­ecule. Intra­molecular O—H...N hydrogen bonds are also present. The discrete hexa­nuclear clusters are further linked through π–π inter­actions into layers parallel to (001), the shortest distance between the centroids of aromatic rings being 3.698 (2) Å.
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